Heterocyclic bases, amination

Heterocyclic bases, amination of, 1, 4 in nucleosides, 55, 1 Heterodienophiles, 53, 2 Hilbert-Johnson method, 55, 1 Hoesch reaction, 5, 9... 

Styphnates. Aromatic hydrocarbons (and also some amines and heterocyclic bases) form 1 1-addition products with styphnic acid (2 4 6-trinitroresorcinol),... 

The most versatile derivative from which the free base can be readily recovered is the picrate. This is very satisfactory for primary and secondary aliphatic amines and aromatic amines and is particularly so for heterocyclic bases. The amine, dissolv in water or alcohol, is treated with excess of a saturated solution of picric acid in water or alcohol, respectively, until separation of the picrate is complete. If separation does not occur, the solution is stirred vigorously and warmed for a few minutes, or diluted with a solvent in which the picrate is insoluble. Thus, a solution of the amine and picric acid in ethanol can be treated with petroleum ether to precipitate the picrate. Alternatively, the amine can be dissolved in alcohol and aqueous picric acid added. The picrate is filtered off, washed with water or ethanol and recrystallised from boiling water, ethanol, methanol, aqueous ethanol, methanol or chloroform. The solubility of picric acid in water and ethanol is 1.4 and 6.23 % respectively at 20°. 

The common impurities found in amines are nitro compounds (if prepared by reduction), the corresponding halides (if prepared from them) and the corresponding carbamate salts. Amines are dissolved in aqueous acid, the pH of the solution being at least three units below the pKg value of the base to ensure almost complete formation of the cation. They are extracted with diethyl ether to remove neutral impurities and to decompose the carbamate salts. The solution is then made strongly alkaline and the amines that separate are extracted into a suitable solvent (ether or toluene) or steam distilled. The latter process removes coloured impurities. Note that chloroform cannot be used as a solvent for primary amines because, in the presence of alkali, poisonous carbylamines (isocyanides) are formed. However, chloroform is a useful solvent for the extraction of heterocyclic bases. In this case it has the added advantage that while the extract is being freed from the chloroform most of the moisture is removed with the solvent. 

N— compounds used as acid inhibitors include heterocyclic bases, such as pyridine, quinoline and various amines. Carassiti describes the inhibitive action of decylamine and quinoline, as well as phenylthiourea and dibenzyl-sulphoxides for the protection of stainless steels in hydrochloric acid pickling. Hudson e/a/. refer to coal tar base fractions for inhibition in sulphuric and hydrochloric acid solutions. Good results are reported with 0-25 vol. Vo of distilled quinoline bases with addition of 0 05m sodium chloride in 4n sulphuric acid at 93°C. The sodium chloride is acting synergistically, e.g. 0-05m NaCl raises the percentage inhibition given by 0-1% quinoline in 2n H2SO4 from 43 to 79%. Similarly, potassium iodide improves the action of phenylthiourea . 

Pyridine (and quinoline) which in so many respects are aromatic and comparable to benzene, lose this character completely on hydrogenation to piperidine (and hydroquinoline), which are entirely of the same nature as secondary aliphatic amines. The completely hydrogenated heterocyclic bases undergo degradation reactions which have become important particularly in the investigation of the constitution of alkaloids. A. W. Hofmann s method of opening rings by means of exhaustive methylation may be illustrated with piperidine. By thermal decomposition of the quaternary ammonium base a C—N-link-age is broken and at the same time water is eliminated. 

The Amination of Heterocyclic Bases by Alkali Amides M. T. Leffler, Org. React., 1942, 1, 91-104. 

Cockram and Wheeler, 1927, 1931 Blayden et al 1948 Wender et al., 1981). These studies, as well as later work (Dryden, 1950, 1951 Given, 1984), showed that significant yields of extracts, often as high as 35 to 40%, can be obtained by using pyridine, certain heterocyclic bases, or primary aliphatic amines (which may, but need not, contain aromatic or hydroxyl substituents). Secondary and tertiary aliphatic amines are often much less effective insofar as more than one alkyl group on the amine appears to present steric problems that interfere with the interaction between the solvent and the coal. 

The reaction of 2,4-dinitrohalobenzenes (F,Cl,Br,I) with the anions of heterocyclic ketene aminals was reported to give arylated products by the S l mechanism. This proposal was based on ESR spectroscopy, ESR spin trapping with nitroso-/-butane and the inhibition of the reaction by FeCl3182. 

Many heterocyclic bases can be oxidized to A-oxides with sodium perborate and acetic acid in the absence of metal catalysts.352 Use of a smaller excess of oxidant leads to diazo compounds.353 Aliphatic amines can be converted to nitroso products. Sodium perborate/acetic acid systems can also cleave hydra-zones, regenerating carbonyl compounds which have been protected by hydrazine formation.354... 

The impetus for the development of synthesis and characterization of complexes of lanthanides with organic nitrogen donor ligands is due to the search for more efficient luminescent rare earth compounds. One of the difficulties is the risk of precipitating lanthanide hydroxides in the process of synthesis of lanthanide complexes with organic amines. In the early stages, lanthanide complexes of heterocyclic bases of low basicities were prepared in aqueous alcoholic media [224], In the synthesis section it was appropriately pointed out the need for the anhydrous conditions and involved procedures for the preparation of lanthanide complexes of ligands of non-ionizable nature. Some representative complexes of both aliphatic and aromatic amines are listed in Table 4.19. 

The heterocyclic hemi-aminal 44 was formed as a model for the synthesis of the marine alkaloids zoanthamine and zoanthenol and is derived from the cyclic imine formed by the reduction of an appropriated substituted azide <07H(72)213>. A pyrrolidine-fused azepine has been isolated from the venom of the ant Myrmicaria melanogaster and assigned as 45 based upon GC and FT-IR comparison with synthetic material <07JNP160>. The axially chiral doubly bridged biphenyl azepine 46 has been synthesised and used with oxone as an epoxidation catalyst in a biphasic system <070BC501>. 

Ring transformation of 2-amino-3-phenacyl-l,3,4-oxadiazolium halides with amines, liquid ammonia, or heterocyclic bases yields 2-amino-l-acylamino-4-arylimidazoles.145... 

IPC-MS/MS was used to quantify heterocyclic aromatic amines in meat-based infant foods [30], The separation of biogenic amines was chemometrically optimized when they were determined in wines [31] a sensitive and selective method to determine 12 biogenic amines regardless of the characteristics of the vegetal food matrix was successfully validated [32], Determination of soybean proteins in commercial products was performed by fast IPC using an elution gradient and acetic acid as the IPR [33],... 

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